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WO2024128745A1 - Procédé de production d'hydrogène propre - Google Patents

Procédé de production d'hydrogène propre Download PDF

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WO2024128745A1
WO2024128745A1 PCT/KR2023/020386 KR2023020386W WO2024128745A1 WO 2024128745 A1 WO2024128745 A1 WO 2024128745A1 KR 2023020386 W KR2023020386 W KR 2023020386W WO 2024128745 A1 WO2024128745 A1 WO 2024128745A1
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sodium sulfate
gas
ammonia
hydrogen
carbon dioxide
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Korean (ko)
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변영철
장진호
민정기
유종근
김은애
박현수
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Research Institute of Industrial Science and Technology RIST
Posco Holdings Inc
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Research Institute of Industrial Science and Technology RIST
Posco Holdings Inc
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Priority to JP2025523052A priority Critical patent/JP2025538101A/ja
Priority to CN202380076437.0A priority patent/CN120152936A/zh
Priority to EP23903948.0A priority patent/EP4635907A1/fr
Publication of WO2024128745A1 publication Critical patent/WO2024128745A1/fr
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    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D7/00—Carbonates of sodium, potassium or alkali metals in general
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0211—Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step
    • C01B2203/0216—Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step containing a non-catalytic steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/042—Purification by adsorption on solids
    • C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1258—Pre-treatment of the feed
    • C01B2203/1264—Catalytic pre-treatment of the feed
    • C01B2203/127—Catalytic desulfurisation

Definitions

  • One aspect of the present invention is to produce sodium bicarbonate and gypsum (CaSO 4 ) using carbon dioxide generated through steam reforming of natural gas containing methane and sodium sulfate generated as an industrial by-product, which is environmentally friendly and 2 for the treatment of industrial by-products.
  • the goal is to provide a method for producing clean hydrogen that is economically feasible as it does not require the cost of a car.
  • Figure 1 shows an exemplary overall process diagram for producing clean hydrogen using methane.
  • Figure 2 shows the results of XRD analysis of sodium bicarbonate (left) and gypsum (right) produced in the process proposed by an embodiment of the present invention.
  • Figure 3 is a graph of sodium bicarbonate yield according to water/waste weight ratio and NH 3 /Na + molar ratio.
  • Figure 4 is a graph of sodium bicarbonate purity and yield according to NH 3 /Na + molar ratio.
  • a methane reforming step of converting methane-containing gas into a reformed gas containing hydrogen, CO, and CO 2 through a reforming reaction using steam; Obtaining a hydrogen and carbon dioxide mixed gas by performing a water-gas shift (WGS) on the reformed gas; A separation step of separating hydrogen and carbon dioxide from the mixed gas; and mixing the separated carbon dioxide with sodium sulfate, ammonia, and water.
  • WGS water-gas shift
  • the methane reforming step which converts methane-containing gas into reformed gas containing hydrogen, CO, and CO 2 through a reforming reaction using steam, produces reformed gas containing hydrogen and carbon monoxide (CO) through a reforming reactor using steam. It can be performed by doing this.
  • the steps to remove sulfur include a catalytic removal method that heats the exhaust gas and removes metal oxides such as ZnO, CuO, and MoO, a flue gas absorption method that absorbs SO 2 into water to generate H 2 SO 4 , and a method of removing sulfur using limestone (CaCO). 3 ) It can be performed by the lime method in which Ca 2+ and SO 2 react to produce CaSO 4 and the Trona method in which sodium bicarbonate (NaHCO 3 ) is added to produce sulfur, but the method for removing sulfur is not particularly limited. No.
  • the reformed gas is subjected to water-gas shift (WGS) to obtain a mixed gas of hydrogen and carbon dioxide.
  • WGS water-gas shift
  • the water gas conversion is a process of generating hydrogen by reacting carbon monoxide with water vapor, and the reaction equation is as follows.
  • Hydrogen can be obtained by separating hydrogen from the hydrogen and carbon dioxide mixed gas obtained through this process.
  • the separation of hydrogen and carbon dioxide is, for example, a Pressure Swing Adsorption (PSA) process that selectively adds an adsorbent that reacts with CO 2 or H 2 and produces high-purity hydrogen through changes in operating pressure, depending on the size of the gas molecule.
  • PSA Pressure Swing Adsorption
  • sodium bicarbonate can be produced by mixing carbon dioxide separated from the mixed gas with sodium sulfate, ammonia, and water.
  • a step of mixing separated carbon dioxide, sodium sulfate, ammonia, and water is performed, and the mixing step is a mixing step of countercurrently mixing carbon dioxide into the mixed solution obtained by mixing the sodium sulfate solution and the aqueous ammonia solution. It may be performed including.
  • the sodium sulfate solution may be a solution obtained by solid-liquid separation of a sodium sulfate-containing material with a sodium sulfate content of 50% by weight or more.
  • the present invention increases the purity of the produced sodium bicarbonate by removing undissolved impurities in producing sodium bicarbonate by reacting carbon dioxide and sodium sulfate-containing materials (waste) in this step, and ammonia is removed even in the high pH state of the solution due to the characteristics of the waste.
  • a method for efficiently mixing to dissolve carbon dioxide and generate sodium bicarbonate is provided.
  • the mixing step may be performed by mixing a sodium sulfate solution and an aqueous ammonia solution and mixing carbon dioxide into the mixed solution in a countercurrent manner.
  • the sodium sulfate solution may be obtained by dissolving a sodium sulfate-containing material, for example, a sodium sulfate-containing material such as a desulfurization by-product, in an eluent, and may be obtained using a material containing 50% or more of sodium sulfate.
  • a sodium sulfate-containing material for example, a sodium sulfate-containing material such as a desulfurization by-product
  • sodium sulfate-containing waste may be generated by desulfurizing exhaust gas containing sulfur oxides (SOx) with sodium bicarbonate, or it may be a waste generated as a by-product in a lithium production plant.
  • the waste containing sodium sulfate may contain eluted heavy metal components such as lead (Pb) and zinc (Zn), and has a high content of alkaline components such as sodium (Na), potassium (K), and calcium (Ca). It is characterized by a high content of chlorine (Cl).
  • Pb lead
  • Zn zinc
  • alkaline components such as sodium (Na), potassium (K), and calcium (Ca). It is characterized by a high content of chlorine (Cl).
  • Most of the sodium bicarbonate used as a desulfurization agent reacts with SOx and is converted into sodium sulfate, and it also contains some insoluble gangue components contained in the exhaust gas.
  • the main crystalline phases constituting the desulfurization waste are sodium sulfate, sodium chloride and potassium chloride, sodium carbonate, calcium sulfate and calcium carbonate, and include iron oxide.
  • the main crystal phases of the desulfurization dust aqueous solution sodium sulfate, sodium chloride, and potassium chloride are highly soluble in water, so an alkaline aqueous desulfurization dust solution can be prepared by dissolving in water.
  • the sodium sulfate-containing material of the present invention may be a desulfurization by-product.
  • the eluent is not particularly limited as long as it is a material capable of eluting sodium ions in contact with a sodium sulfate-containing material, but may be, for example, one or more selected from water and an aqueous ammonia solution, for example, water.
  • the ratio of the sodium sulfate-containing waste and the eluent is important, and if the ratio of the eluent is too low, the sodium sulfate waste will be completely destroyed. Since it does not dissolve, a lot of residue is generated, which reduces the recovery rate of sodium.
  • the ratio of the eluent at which sodium sulfate is not lost as a residue is 1.2 parts by weight or more of the eluent relative to 1 part by weight of the sodium sulfate waste.
  • 1.4 to 3 for example, 2 to 3 parts by weight of the eluent is mixed relative to 1 part by weight of the sodium sulfate waste, and if the eluent is contained in excess beyond this range, carbon dioxide is then dissolved in the sodium-containing solution. Even if it is allowed to do so, it does not precipitate into sodium bicarbonate, and therefore the content of sodium bicarbonate discharged in a dissolved state in the solution is high, resulting in a low sodium bicarbonate recovery rate.
  • the recovery rate of sodium bicarbonate can be adjusted by adjusting the mass ratio of the sodium sulfate-containing material and water as an eluent.
  • the mass ratio of the sodium sulfate-containing material and the eluent added may be 1:1.4 to 1:3. If the mass ratio of the eluent to the sodium sulfate-containing material is less than this range, the sodium sulfate does not dissolve and the sodium sulfate is lost as a residue, which may tend to reduce the recovery rate of sodium ions.
  • the mass ratio of the eluent to the sodium sulfate-containing material is 3.
  • sodium bicarbonate production method of the present invention When the sodium sulfate solution obtained by this ratio of sodium sulfate-containing waste and the eluent is applied to the sodium bicarbonate production method of the present invention, more than 60% of the sodium in the sodium sulfate-containing waste can be recovered as sodium bicarbonate.
  • the pH range in which bicarbonate ions are most generated is pH 7-10, for example, 7.5-9, and more preferably between pH 8-9, so in order to increase the production efficiency of sodium bicarbonate, it is best to maintain the pH between 8-9. desirable.
  • the pH exceeds 10
  • basic ammonia may not be sufficiently dissolved, and if the pH is lower than this, hydrogen carbonate ions (HCO 3 - ) may be converted to carbonic acid (H 2 CO 3 ) and the sodium bicarbonate production rate may decrease. there is.
  • sodium bicarbonate can act as a pH buffer.
  • the yield of sodium bicarbonate can be improved by mixing ammonia, for example, with sodium sulfate solution in the form of an aqueous ammonia solution.
  • the sodium sulfate solution and ammonia aqueous solution have an ammonia (NH 3 )/sodium (Na + ) molar ratio of 0.8 to 1.5, preferably more than 0.6 and 1.3 or less. , for example, is mixed so that it is 0.7 or more and 1.2 or less.
  • ammonia is essential in the process of producing sodium bicarbonate by injecting carbon dioxide from sodium sulfate-containing waste can be understood from the thermodynamic information below.
  • the recovery rate of sodium bicarbonate decreases, and if the molar ratio increases, the recovery rate of sodium bicarbonate increases, but the purity of sodium bicarbonate may decrease.
  • the ratio of ammonia (NH 3 )/sodium (Na + ) is 0.6 or less, the yield of sodium bicarbonate may decrease because it is lower than the optimized pH range for producing sodium bicarbonate, and the pH If it is 1.5 or more, the yield is high, but a large amount of impurities such as (NH 4 ) 2 SO 4 are produced and the purity of sodium bicarbonate may be reduced.
  • the preferred ammonia (NH 3 )/sodium (Na + ) ratio is 1.25 to 1.35.
  • the free energy of reaction A ( ⁇ G, 298 K) is 160.653 kJ/mol, and the free energy of reaction B ( ⁇ G, 298 K) is 42.702 kJ/mol.
  • reaction A using only sodium sulfate and carbon dioxide, the value is positive, so it is not a spontaneous reaction, but when ammonia is added, the value is negative, confirming that it is a spontaneous reaction. Therefore, it can be confirmed that ammonia, which acts as a pH buffer, is required when producing sodium bicarbonate using sodium sulfate.
  • the mixing step of mixing a sodium sulfate solution and an ammonia aqueous solution to obtain a mixed solution may be performed at a temperature of 25°C or more and less than 100°C. If the temperature is outside this range, the solubility of sodium sulfate tends to decrease. This may lower the yield.
  • Ammonia that can be used in the present invention may be ammonia or a mixed solution containing ammonia, a mixed gas, or a solid, for example, an ammonia aqueous solution.
  • the present invention performs a step of mixing a sodium sulfate solution and an aqueous ammonia solution to obtain a mixed solution, followed by a mixing step of countercurrently mixing a gas containing carbon dioxide into the mixed solution.
  • high-efficiency sodium bicarbonate can be produced by maximizing the contact area between the sodium sulfate solution and carbon dioxide and increasing the dissolution of carbon dioxide.
  • sodium bicarbonate may be generated through the reaction between sodium ions in the solution and bicarbonate ions (HCO 3 - ) generated by carbon dioxide.
  • the carbon dioxide used at this time may be pure carbon dioxide or a nitrogen mixed gas containing 10 to 30% by volume of carbon dioxide, for example, FINEX off gas (FOG), FINEX tail gas (FTG), Blast furnace gas (BFG), converter gas, coal power plant off-gas, gas power plant off-gas, incinerator off-gas, glass melting off-gas, thermal facility off-gas, petrochemical process off-gas, petrochemical process process gas, pre-combustion off-gas and gasifier off-gas. It may be one or more selected from the group consisting of. Additionally, in order to increase the concentration of carbon dioxide, carbon dioxide can be concentrated and used using wet amine method, separation membrane method, dry pressure swing adsorption and desorption method, etc.
  • the reaction pressure of the sodium bicarbonate production reactor in which the carbonation reaction occurs may be 1 to 10 atm, and the reaction temperature may be 50°C or less. If the pressure of the carbonation reactor exceeds 10 atm, a sufficient amount of carbon dioxide can be dissolved, but the energy required for the carbonation reactor is high, which reduces the economic feasibility of the final product, sodium bicarbonate.
  • the time of the carbonation reaction may vary depending on the carbon dioxide injection method. When carbon dioxide is injected in the form of gas, it varies depending on the presence or absence of aeration, and if aeration is performed, it may be possible for less than 4 hours. However, the optimized pressure and reaction time may vary depending on the size/space/conditions of the reactor.
  • the sodium sulfate solution of the present invention may be a solution obtained by separating a liquid sodium sulfate-containing material with a sodium sulfate content of 30% by weight or more into solid and liquid, that is, by separating solid and liquid.
  • the solid-liquid separation device is not particularly limited, and any device that can separate the solid phase and the liquid phase can be used.
  • gypsum (CaSO 4 ) can also be produced by adding a calcium-containing material to the filtrate.
  • the calcium-containing material is selected from the group consisting of waste cement, waste concrete, coal ash, fly ash, iron slag, low or high grade quicklime (CaO), calcium chloride (CaCl 2 ), wollastonite, limestone, olivine, serpentine, asbestos, and deinked ash. There may be more than one.
  • the purity of gypsum is low, the purity of gypsum can be increased by recovering ammonia and adding sulfuric acid and gypsum to the remaining filtrate.
  • the ammonia aqueous solution injected into the mixing reactor where the ammonia aqueous solution and the sodium sulfate solution are mixed to obtain a mixed solution is preferably injected at a flow rate of 2.5 to 5 L/min. If the flow rate is less than the above range, the residence time of the solution is too long. There is a problem that it is difficult to obtain a sufficient reaction surface area because the solution stagnates because it is too long, and even if it exceeds this, there is a problem that a sufficient reaction does not occur because the residence time of the solution is too short.
  • the carbon dioxide-containing gas is preferably injected at a flow rate of 2.5-5 L/min. If the flow rate is less than the above range, there is a problem that the gas is not smoothly transported to the end of the reactor due to the low discharge pressure. If it exceeds this, the gas is not smoothly transported to the end of the reactor. There is a problem that the residence time of the gas is too short and the reaction does not sufficiently occur.
  • a hydrogen production experiment was performed according to the process diagram shown in FIG. 1.
  • the composition of the methane-containing gas used at this time is shown in Table 1 below, and the XRD analysis results of the finally produced sodium bicarbonate are shown in Figure 2.
  • Figure 3 shows the results of sodium bicarbonate produced using carbon dioxide remaining after hydrogen was separated from the mixed gas generated through methane reforming.
  • the recovery rate of sodium bicarbonate produced varies depending on the molar ratio of Na + eluted from ammonia and sodium sulfate-containing waste and the ratio of sodium sulfate-containing waste and water.
  • Methane-containing gas composition Furtherance Methane (CH 4 ) Ethane (C 2 H 6 ) Propane (C 3 H 8 ) Bhutan (C 4 H 10 ) Composition (vol%) 90.09 6.0 2.5 1.1 Furtherance Carbon dioxide (CO 2 ) Nitrogen (N 2 ) oxygen (O 2 ) sulfur Composition (vol%) 0.1 0.2 0 to 2 0.01
  • the methane gas is heated to about 320°C through a pre-heater, and then a desulfurization process is performed.
  • the desulfurization reactor is filled with catalysts such as ZnO, CuO, and MoO. Unsaturated hydrocarbons become hydrogen compounds, and unreacted sulfur components become hydrogen compounds of hydrogen sulfide and are absorbed.
  • the desulfurized methane gas is mixed with water vapor to raise the temperature to 520°C and then passes through the reformer. Basically, the following reaction occurs here.
  • Total heat balance is an endothermic reaction, and comes out after passing through the reformer at a temperature of about 830°C.
  • the reformed gas passes through a WGS (Water Gas Shift) reactor. Changes in gas composition before and after passing through the WGS reactor are shown in Table 2 below. CO reacts with water vapor in the reformed gas to generate hydrogen and CO 2 .
  • the produced mixed gas goes through a pressure circulation process (PSA) to separate hydrogen and carbon dioxide.
  • PSA pressure circulation process
  • the pressure circulation process proceeds as follows: adsorption process - regeneration process - discharge process - pressurization process, and high purity hydrogen (99.999%) is produced.
  • the separated carbon dioxide is also concentrated to more than 90% through a pressure circulation process.
  • carbon dioxide in order for the produced hydrogen to be recognized as clean hydrogen, carbon dioxide must be used, so in the present invention, sodium sulfate is used together with the carbon dioxide obtained in this way to produce sodium bicarbonate. do.
  • the sodium sulfate-containing waste used in this example was a desulfurization by-product with the composition shown in Table 3 below.
  • Sodium sulfate-containing waste which is a desulfurization by-product, contains inorganic substances as shown in Table 3 above and exhibits a pH of 9 or higher when dissolved in water.
  • ammonia, water, and sodium sulfate are mixed, and carbon dioxide may be additionally mixed therewith.
  • the ammonia, water, and sodium sulfate may be added individually or in a mixed state.
  • the filtrate produced after the carbonation reaction in the carbonation reactor contains a large amount of sulfate ions (SO 4 2- ). Therefore, gypsum (CaSO 4 ) can also be produced by adding a calcium-containing material to the filtrate.
  • ammonia has a high unit price, it is desirable to recover ammonia for economical process operation.
  • the pH of the filtrate from the carbonation reactor is between 7 and 8, and most ammonia exists in the form of ammonium ions (NH 4 + ).
  • the pH must be increased to 10 or higher to recover ammonia in gas form or in the form of water vapor using water vapor. Therefore, quicklime (CaO), a calcium-containing material, is added to increase pH.
  • quicklime a calcium-containing material
  • slaked lime which can increase pH, can be used. More than 90% of the ammonia in the solution can be recovered, and the recovered ammonia is reused in the carbonation reactor.
  • the ions remaining in the solution are calcium (Ca 2+ ) and sulfate (SO 4 2- ). If the pH is higher than 6, it reacts with carbonate (CO 3 2- ) ions remaining in the solution and lime (CaCO 3 ) and slaked lime (Ca(OH) 2 ) are produced as impurities, so it is necessary to reduce the pH to 6 or less. There is. To reduce pH, acid must be added. Sulfuric acid (H 2 SO 4 ) or hydrochloric acid (HCl) can be added. Wastewater from the gypsum extraction reactor is treated through a wastewater treatment process.
  • the water:waste ratio is set to 1.0, 1.5, 2.0, 2.5, 3.0, and 3.5 were prepared and stirred in the first reactor.
  • each eluate was stirred in the second reactor at an ammonia (NH 3 )/sodium (Na + ) ratio of 0.6, 0.8, 1.0, 1.3, and 1.5, and then carbon dioxide was added to the third reactor to start the reaction. .
  • NH 3 ammonia
  • Na + sodium
  • the ammonia (NH 3 )/sodium (Na + ) ratio is less than 0.6, the sodium bicarbonate recovery rate is reduced due to low pH, and if the ammonia (NH 3 )/sodium (Na + ) ratio is higher than 1.5, the sodium bicarbonate yield increases, but ( It can be seen that the purity of sodium bicarbonate decreases due to the formation of impurities such as NH 4 ) 2 SO 4 .

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Abstract

La présente invention concerne un procédé de production d'hydrogène propre et, plus précisément, un procédé de production d'hydrogène propre comprenant : une étape de reformage de méthane consistant à convertir un gaz contenant du méthane en un gaz reformé contenant de l'hydrogène, du CO et du CO2 par l'intermédiaire d'une réaction de reformage à l'aide de vapeur ; une étape consistant à obtenir un gaz mixte d'hydrogène et de dioxyde de carbone en procédant à une réaction du gaz à l'eau (WGS) sur le gaz reformé ; une étape de séparation consistant à séparer l'hydrogène et le dioxyde de carbone du gaz mixte ; et une étape consistant à mélanger le dioxyde de carbone séparé avec du sulfate de sodium, de l'ammoniac et de l'eau.
PCT/KR2023/020386 2022-12-16 2023-12-12 Procédé de production d'hydrogène propre Ceased WO2024128745A1 (fr)

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JP2025523052A JP2025538101A (ja) 2022-12-16 2023-12-12 クリーン水素の製造方法
CN202380076437.0A CN120152936A (zh) 2022-12-16 2023-12-12 用于生产清洁氢气的方法
EP23903948.0A EP4635907A1 (fr) 2022-12-16 2023-12-12 Procédé de production d'hydrogène propre

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KR1020220177485A KR20240094849A (ko) 2022-12-16 2022-12-16 청정 수소의 제조방법
KR10-2022-0177485 2022-12-16

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4137298A (en) * 1977-12-21 1979-01-30 Continental Oil Company Production of a hydrogen-rich gas from a hydrogen, carbon monoxide and carbon dioxide-containing fuel gas
WO1997000829A1 (fr) * 1995-06-23 1997-01-09 Ormiston Mining & Smelting Co. Ltd. Procede pour la production de bicarbonate de sodium, de carbonate de sodium et de sulfate d'ammonium a partir de sulfate de sodium
US20130011323A1 (en) * 2011-07-05 2013-01-10 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Process For The Production Of Hydrogen And Carbon Dioxide Utilizing Magnesium Based Sorbents In A Fixed Bed
KR20210079909A (ko) * 2019-12-20 2021-06-30 한국에너지기술연구원 프리리포머(pre-reformer) 및 분리막 리포머를 이용한 수소 생산 장치 및 공정
WO2021175662A1 (fr) * 2020-03-06 2021-09-10 Reinertsen New Energy As Procédé de production d'hydrogène et/ou d'ammoniac

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4137298A (en) * 1977-12-21 1979-01-30 Continental Oil Company Production of a hydrogen-rich gas from a hydrogen, carbon monoxide and carbon dioxide-containing fuel gas
WO1997000829A1 (fr) * 1995-06-23 1997-01-09 Ormiston Mining & Smelting Co. Ltd. Procede pour la production de bicarbonate de sodium, de carbonate de sodium et de sulfate d'ammonium a partir de sulfate de sodium
US20130011323A1 (en) * 2011-07-05 2013-01-10 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Process For The Production Of Hydrogen And Carbon Dioxide Utilizing Magnesium Based Sorbents In A Fixed Bed
KR20210079909A (ko) * 2019-12-20 2021-06-30 한국에너지기술연구원 프리리포머(pre-reformer) 및 분리막 리포머를 이용한 수소 생산 장치 및 공정
WO2021175662A1 (fr) * 2020-03-06 2021-09-10 Reinertsen New Energy As Procédé de production d'hydrogène et/ou d'ammoniac

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KR20240094849A (ko) 2024-06-25
CN120152936A (zh) 2025-06-13
EP4635907A1 (fr) 2025-10-22

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